Water-insoluble carbonylalkylene sulfonamido containing azo dyestuffs

ABSTRACT

Water-insoluble azo-dyestuffs of the formula   said compounds being suitable for the dyeing or printing of synthetic fibrous materials, such as fibrous materials of celluloseacetates, polyamides, polyurethanes, polyolefins, polycarbonates and, particularly, polyesters, the dyeings obtained on these fibres being distinguished by a very good fastness to wet processing, ironing, waste gas and light and by a very good building up.   and R2 represents hydrogen, lower alkyl, -lower alkylene-OH, lower alkylene-CN,   R1 represents lower alkyl, lower alkylene-OH,   WHEREIN IN WHICH D represents nitro-phenylene, dinitro-phenylene, carbo-lower alkoxy-phenylene, chloro-nitro-phenylene, cyano-nitrophenylene, dichloro-nitro-phenylene, chloro-bromo-nitrophenylene, chloro-dinitro-phenylene, bromo-dinitro-phenylene, chloro-lower alkyl sulfonyl-phenylene, nitro-lower alkylsulfonyl-phenylene, bromo-cyano-nitro-phenylene, chlorotrifluoromethyl-phenylene, phenylazo-phenylene, nitrothiazolyl, carbo-lower alkoxy-thiazolyl or nitrobenzothiazolyl, A represents hydrogen, chlorine, lower alkyl, lower alkoxy or O-lower alkylene-lower alkoxy, B represents hydrogen, chlorine, lower alkyl, lower alkoxy, lower alkyloylamino, benzoylamino,

Y 22 Filed:

United States Patent [191 Schickfluss et al.

[451 May 13, 1975 1 WATER-INSOLUBLE CARBONYLALKYLENE SULFONAMIDO CONTAINING AZO DYESTUFFS [75] Inventors: Rodolf Schickfluss, Frankfurt am Main; Willi Steckelberg, Hofheim, Taunus, both of Germany [73] Assignee: Hoechst Aktiengesellschaft,

Frankfurt am Main, Germany Jan. 30, 1973 [21] Appl. No.: 328,064

[30] Foreign Application Priority Data Feb. 3, 1972 Germany 2205062 [52] U.S. Cl. 260/207.1; 260/152; 260/155; 260/156; 260/157; 260/158; 260/163;

260/556 A; 260/556 AR [51] Int. Cl C09c 29/06; C09c 29/34 [58] Field of Search 260/207, 207.], 174, 177, 3 260/184, 187

[56] References Cited UNITED STATES PATENTS 1,718,882 6/1929 Schwenk et a1 260/207 3,178,405 4/1965 Merian 260/207 3,398,137 8/1968 Mueller 260/20'7 3,483,180 12/1969 Ramanathan 260/207 3,534,016 10/1970 Lange 260/207 3,544,548 12/1970 Gunther et a1. 260/207 3,549,305 12/1970 Renfrew et a1. 260/207 3,552,905 l/l971 Sartori 260/207 3,642,767 2/1972 Hahn et a1. 260/207 3,679,657 7/1972 Desai et al. 260/207 Primary Examiner--Henry R. Jiles Assistant Examiner-Robert W. Ramsuer Attorney, Agent, or Firm-Curtis, Morris & Safford [57] 1 ABSTRACT A water-insoluble azo dyestuff of the formula R D-N=N-- w/ 9 Claims, N0 Drawings WATER-INSOLUBLE CARBONYLALKYLENE SULFONAMIDO CONTAINING AZO DYESTUFFS The present invention relates to new, valuable, wa-' ter-insoluble azo dyestuffs of the general formula (1) in which D represents the radical of a diazo component of the benzene or heterocyclic series which is free from hydrosolubilizing groups, which may be substituted, for example by halogen atoms such as chlorine or bromine atoms, by nitro, cyano, alkyl, alkoxy, alkylsulfonyl, trifluoromethyl, sulfonamido, acyl, phenoxy, carboxylic acid alkyl ester and/or carboxylic acid amide groups, the alkyl and alkoxyl groups containing 1 to about 4 carbon atoms, and, if D represents a phenyl radical, it may also be substituted by a phenylazo group, A represents a hydrogen atom, a halogen atom such as a chlorine or bromine atom, or an alkyl or alkoxy radical which may be substituted by chlorine or bromine atoms, cyano, hydroxy, alkoxy, acyl or acyloxy groups, the alkyl and alkoxy groups containing 1 to about 4 carbon atoms, B represents a hydrogen atom, a halogen atom such as a chlorine or bromine atom or an alkyl, alkoxy, acylamino radical which may be substituted by chlorine or bromine atoms, cyano, hydroxy, alkoxy, acyl or acyloxy groups or a side chain of the formula in which Y represents a hydrogen atom or an alkyl or benzyl group or an aryl group which may be substituted by alkyl, alkoxy, acyl or acyloxy groups or halogen atoms such as chlorine or bromine atoms, Z represents an alkyl group or an aryl group which may be substituted by chlorine or bromine atoms, alkyl, alkoxy or nitro group or acyl groups, and n represents an integer from 1 to 6, and R represents a hydrogen atom or an alkyl, acetyl or benzoyl group (the alkyl and alkoxy groups standing for B, Y, Z and R containing 1 to about carbon atoms), and R and R represent hydrogen atoms or alkyl radicals of l to about 4 carbon atoms which may be substituted by chlorine or bromine atoms, cyano, hydroxy, alkoxy, acyl or acyloxy groups or side chains of the afore-mentioned formula (2) which are bound over the bridging member alkyleneO- or provided that the dyestuff molecule contains once or twice the side chain of the specified formula (2).

By acyl groups, there have to be understood alkyloyl groups containing 2 to about 10 carbon atoms such as the acetyl group and furthermore the benzoyl group, by acyloxy groups there have to be understood alkyloyloxy groups containing 2 to about 10 carbon atoms such as the acetoxy group and furthermore the benzoyloxy group, and by acylamino groups there have to be understood aliphatic alkyloylamino groups containing 2 to about 10 carbon atoms for example the acetylamino group or the benzoylamino group.

If D stands for a heterocyclic radical, it may represent for example a thiazole, benzothiazole, thiadiazole, pyridine, quinoline, pryazole, indazole, triazole or phthalimide radical.

As diazo components D-NH on which the dyestuffs of the formula (1) are based, there may be mentioned, for example: aniline, 4-fluoroaniline, 2- chloroaniline, 4-bromoaniline, 2,4,5-trichloroaniline, 4-nitraniline, 3-nitraniline, 2-chloro-4-nitraniline, 2- bromo-4-nitraniline, 2-chloro-4-sulfonamidoaniline, 2,4-dichloroaniline, 2-cyano-4-nitraniline, 2,4- dinitraniline, 6-chloro-2,4-dinatraniline, 6-bromo-2,4- dinitraniline, 2,6-dichloro-4-nitraniline, 4-nitro-2- methylsulfonybaniline, 4-amino-acetophenone, 5-nitro-2-aminobenzophenone, 4-acetamino-aniline, 4-amino-benzoic acid ethyl ester, 2-amino-benzoic acid-n-butyl ester, 2-bromo-6-cyano-4-nitraniline, 4-methyl-2-nitraniline, 4-phenylazoaniline, Z-methoxy- 4-(4-nitrophenylazo)-aniline, 2-carbomethoxy-4- nitroaniline, 3-nitro-4-aminoanisole, 4-cyano-2- nitraniline, 4,6-dichloro-2-nitraniline, 2-chloro-4- amino-anisole, 5-chloro-2-amino-anisole, 2,6-dinitro- 3-amino-4-methoxy-toluene, 3-nitro-4-amino-benzotrifluoride, 2-aminothiazole, 5-nitro-2-amino-thiazole, 5 -carbethoxy-2-aminothiazole, 6-ethoxy-2-aminobenzothiazole, 6-ethylsulfonyl-2-amino-benzothiazole, 5-cyano-2-amino-thiazole, 5-nitro-4-methyl-2-aminothiazole, 4 methyl-2-aminothiazole, 4 phenyl-2- aminothiazole, 6-chloro-2-amino-benzothiazole, 6- cyano-2-amino-benzothiazole, benzothiazole, Z-amino- 1 ,3 ,4-thiadiazole, 3- aminopyrazole, 3-aminopyridine and B-aminoindazole.

Particularly valuable novel dyestuffs encompassed by the general formula (1) are those which correspond to the general formula (3).

(R has here the meaning given above) and D, A, R Y, Z and n have the meanings given above and B has the meaning given here-above for B, provided that B does not contain a side chain of the formula 2), and R rep- 6-nitro-2-aminoresents an alkylene group of 2 to 4 carbon atoms, for

example theethylene or propylene group. 1 Further particularly valuable novel dyestuffs encompassed by the formula (1 are those which correspond to the general formula SO Z in which D, A, Y, Z and nhave the meanings given above, R and R have the meanings given above for R, and R provided that R, and R do not contain a side chain of the general formula (2), and R represents a hydrogen atom or an acetyl group.

The novel dyestuffs designated asbeing particularly valuable and corresponding to the above-specified general formula (3) and (4) are distinguished by particularly good properties of fastness to sublimation in the dyeing and printing of synthetic fibrous materials. The present invention furthermore relates a. to a process for the manufactureof dyestuffs of the general formula (1 wherein a diazo component of the general formula (5) D' NH in which D has the meanings given above, is diazotized,

in which A, B, R,, R X, Y, Z and n have the meanings given above, in the manner described, for example.

under (a),

c. to a process for the manufacture of dyestuffs of the general formula (4), wherein a diazo component of the general formula (5) is diazotized, for example in the manner described under (a) and coupled with a coupling component of the general formula (8) in which A, R, R R Y, Z and n have the meanings for example with sodium nitrite and a mineral acid or v a with a solutionof nitrosyl-sulfuric acid in concentrated sulfuric acid, and coupled with a coupling component of the general formula (6) tate, magnesium carbonate or pyridine, theaddition of g which may often be of advantage.

b. to a process for the manufacture of dyestuffs of the general formula (3 wherein a diazo component of the general formula (5) is diazotized, for example in the manner described under (a).an'd coupled with a coupling component of the general formula (7) given above, in the manner described, for example under (a), and

d. to a process for the manufacture of dyestuffs of the general formula (3), wherein a dyestuff of the general formula (9) in which D, A, B, R R and X have the meanings given above, is acylated with a carboxylicacid of the general formula (10) so -z in which Y, Z and n have the meanings given above, or

preferably with a functional derivative of such an acid, for example and acid anhydride or an acid halide such as the'acid bromide or, preferably the acid chloride, at

temperatures in the range of from about 20C to about C, suitably in an inert organic solvent and optionallyin'the presence of an acid-binding agent.

As acid-binding agent, there is preferably used pyridine, a mixture of pyridine bases, quinoline or also a low molecular trialkyl-amine, for exampletri'ethylamine. When using a halide of the acid of the mentioned formula it is of advantage to add an acid-binding agent to the esterification mixture. As inert organic solvents, there may be used, for example hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, methylene chloride, trichloroethylene, chlorobenzene, bromobenzene, ketones such as acetone, methyl-ethyl ketone, methyl-isobutyl ketone, furthermore esters such as di-ethyl ether, di-isopropyl ether, dioxane, 1,2- dimethoxyethane, methoxyor ethoxy-benzene, as well as sulfolane (tetramethylenesulfone).

The dyestuffs are obtained in water-insoluble form and isolated, for example by filtration and freed from adhering electrolytes by washing with water.

Instead of a uniform diazo component, there may be used in the mentioned process variants (a), (b) and (c) also a mixture of two or more diazo components and instead of the uniform coupling component a mixture of two or more coupling components.

The novel dyestuffs are suitable either alone or as mixtures with each other or with other dyestuffs, preferably in the form of a preparation, for example in an aqueous dispersion or in solutions with organic solvent or in emulsions or dispersions which contain a solvent or a mixture of solvents also water, for the dyeing or printing of synthetic fibrous materials, for example fibers of cellulose di-acetate, 2 /2-acetate and triacetate, polyamides such as polye-caprolactam or polyhexamethylenediamine-adipate, polyurethanes, polyolefins,

polycarbonates, in particular, however polyesters such as polyethylene terephthalates.

For the dyeing or printing, the above-mentioned synthetic fibrous materials may also be present in admixture with one another or with natural fibrous materials such as cellulose fibres or wool. For dyeing, they may be present in various processing stages, for example as combed material, as flocks, filaments, fabrics or knit fabrics.

The dyestuffs of the invention are applied in known manner, in general from an aqueous dispersion, but also from organic solvents. The dyestuffs can be dispersed, for example, by grinding them in the presence of a dispersing agent, for example the condensation product of formaldehyde and a naphthalene-sulfonic acid.

Otherwise, the dyeing conditions depend largely on the nature of the synthetic fibrous materials and their processing stage. i

The dyeing of shaped bodies of cellulose acetate is effected, for example, in a temperature range of from 75 to 85C. Cellulose triacetate fibers are dyed at temperatures between about 90 and 125C. The dyestuffs are applied onto polyamide fiber materials in the temperature range of from about 90 ato 120C, For the dyeing of fibrous materials of polyesters, the methods known for this purpose are used, i.e. by dyeing the fibrous material in the presence of carriers such as o or p-phenylphenol, methylnaphthalene or methyl salicylate, at temperature of about 100 to about 130C or,

if no carriers are used, at correspondingly higher temperatures, for example at temperatures between 120 and 140C. Furthermore, the dyestuffs may be applied by padding while using or not a thickener, for example tragacanth thickener, and fixed by the action of heat, for example dry heat or steam, for about one-half to 30 minutes at temperatures in the range of from about to 230 In order to improve the fastness to rubbing, the material so dyed is then freed from dyestuff adhering to the surface, for example by rinsing or by a reductive after-treatment. This after-treatment is generally carried out at 60 to C in a bath which contains aqueous sodium hydroxide solution, sodium dithionite and a non-ionic detergent, for example an addition product of ethylene oxide and phenol.

For dyeing the synthetic fibrous materials from organic solvents, the dyestuff is allowed to be absorbed onto the fiber from the solution at room temperature or an elevated temperature, for example at a temperature in the range of from about 70 to C, if desired under pressure, or in a continuous method of operation, the fabrics or knit fabrics are impregnated with a dyestuff solution, dried and subjected for a short time to the action of heat, for example to a temperature in the range of from 180 to 210C. For the exhaust process, there may be mentioned, as solvents, for example solvents which are immiscible with water and have a boiling point in the range of from 40 to 170C, for example aliphatic halogenated hydrocarbons such as methylene chloride, trichloroethane. For a continuous dyeing method, there may also be used solvents which are miscible with water, for example alcohols or dimethylformamide. The solvents may, of course, also be used in the form of mixtures and contain other auxiliary agents which are miscible in solvents, for example oxalkylation products of fat alcohols, alkyl phenols and fatty acids.

For preparing prints on synthetic fibrous materials, for example of polyesters, polyamides or cellulose triacetate, the dyestuffs of the invention are applied in the form of water-containing preparations which may contain, in addition to the finely distributed dyestuff, suitable thickeners and fixing accelerators. Fixation is effected after printing and drying, for example by steaming at atmospheric pressure'or under elevated pressure of up to 2.5 atmospheres gauge pressure for 10 to 60 minutes. Fixation can also be effected by the action of hot air of to 210C during 30 seconds to 10 minutes.

In this manner the novel dyestuffs permit the production on the said synthetic fibrous materials of intense dyeings which have very good fastness to wet processing, to sublimation, to exhaust gases and to light and which have a very good build-up. When used for the dyeing of mixed fabrics of polyester fibers and wool,

EXAMPLE 1 Dyestuff of the formula 0 H -OCQCH BI a. Preparation of the coupling component 33 g (0.2 mole) of N-ethyl-N-oxethyl-aniline were dissolved in 150 ml of anhydrous benzene, combined with. 16 ml of pyridine, and then a solution of 50 g of N-phenyl-sulfone-N-methyl-amino-acetic acid chloride, which had beenobtained by the reaction of benzene sulfochloride with methylaminoacetic acid and following conversion into the acid chloride with thionyl g of 40% by weight nitrosyl-sulfuric acid.

The diazo solution was added dropwise, while well cooling, to a solution of 37.6 g (0.1 mole) of the coupling component that had been prepared as described in 400 ml of glacial acetic acid and 400 ml of ice water. Stirring was continued for 2 hours in order to complete coupling and the pl-l-value was adjusted to 5.5 by the addition of sodium acetate. The dyestuff which had precipitated and corresponded to the above formula was filtered off with suction, washed with water until it was free from salt and acid and dried.

When applied from an aqueous dispersion or from a solution in an organic solvent, the dyestuff yielded ruby red dyeings and prints on polyester and cellulose acetate fibers which had excellent properties of fastness.

On polyam'ide fibers violet red dyeings were obtained which likewise had very good fastness properties.

1 EXAMPLE 2 Dyestuff of the formula 37.6 g (0.2 mole) of 4-nitro-ani1ine were dissolved in 150 ml of 5 N-hydrochloric acid by heating and poured, while stirring, into a mixture of 1 liter of water, 40 ml of SN-aqueous sodium nitrite solution and 500 g of ice.

The diazo solution so obtained was then added dropwise to a solution of 33 g (0.2 mole) of N-ethyl-N-B- oxethyl-aniline in 1 liter of water and 100 ml of 5N- hydrochloric acid. ,Stirring was continued for 2 hours at l5C in order to complete coupling and the pH- value was then adjusted to 5.5 by the addition of sodium acetate. The dyestuff that had precipitated and corresponded to the formula 0 on N vN/ICZHS." 2 *7 I V w v H -OH- was filtered off with suction, washed with water until it was free from salt and neutral and dried.

33.9 g (0.1 mole) of the dyestuff of the abovespecified formula were dissolved in l literof benzene and 9 ml of pyridine and'acylated by the dropwise addition of a solution of 27 g. (0.11 mole) of N- 5 phenylsulfone-N-methyl-aminoacetic acid chloride in 50 ml of benzene and following heating. After removal of the'solvent, the dyestuff of the formula 0 53 c n -ocwca n was isolated and yielded on polyester fibers yellowish red dyeings that had very goodproperties of fastness.

EXAMPLE 3 Dyestuff of the formula ,co-ca sx i e j 2"" a. Preparation of the coupling component 27.2-g (0.2 mole) of S-amino-dimethylaniline were 4 dissolved in 200 ml of chloroform and 18 g of pyridine (0.22 mole). 54.4 g of N-phenylsulfone-Nsmethylaminoacetic acid chloride dissolved in 100 ml of chloroform were added dropwise. The mixture was heated for 5 hours to the boiling temperature under reflux. After having allowed the reaction mixture to cool, it was extracted with .water, dried with calcium chloride and the organic solvent was completely removed by evaporation. The residue was used as cpupling component.

b. Preparation of the dyestuff a 17.2 g (0.1 mole) of 2-chloro-4mitraniline were dissolved in ml of concentrated sulfuric acid and diazotized at 10C with'31.8 g of 40% nitrosyl-sulfuric acid.

55 Stirring was then continued for minutes in order to complete the reaction. 4

34.7 g (0.1 mole) of the above coupling component" EXAMPLE 4 Dyestuff of the formula w. s N-CO-Cli -N I. R Cl 3 l5 R H and -COCH a. Preparation of the coupling component 27.2 g (0.2 mole) of 3-amino-dimethylaniline were dissolved in 200 ml of chloroform and 18 g of pyridine (0.22 mole). Then, 54.4 g of N-phenylsulfone-N-methyl-aminoacetic acid chloride (0.22 mole), dissolved in 100 ml of chloroform, were added dropwise. The mixture was heated for 5 hours to the boiling temperature under reflux. After having allowed the reaction mixture to cool, it was extracted with water, dried with calcium chloride and the organic solvent was completely removed by evaporation. The residue, constituting the 3-( N '-phenylsulfone-N '-methylamino-acetyl)-amino- N,N-dimethylaniline, was dissolved in 100 ml of acetanhydride and heated for 5 hours under reflux. After having cooled, the reaction solution could be used directly for the coupling reaction.

b. Preparation of the dyestuff 16.3 g (0.1 mole) of 2-cyano-4 -nitraniline were dissolved in ml of concentrated sulfuric acid and diazotized at 5C with 31.8 g of 40% nitrosyl-sulfuric acid. Stirring was continued for minutes in order to complete the reaction.

0.1 mole of a solution of the above coupling component were diluted with 200 ml of water and 200 ml of glacial acetic acid. The above-mentioned diazo component was added dropwise, while cooling externally and adding ice. Subsequently, ice was added and stirring was continued for 3 hours in order to complete the coupling reaction. The dyestuff precipitated in crystalline form. it was filtered off with suction; washed until neutral and dried. I yielded on polyester fibers a violet dyeing that had very good properties of fastness.

The dyestuffs of the formula (1) indicated in the following Table were obtained in a manner similar to that described in the foregoing Examples and yielded on polyester fibers the indicated shades which had good properties of fastness.

N .lower alkyl -lower alkylene-O-LO-lower alkylene- 1 Q '0 2 lower alkyl providing that at least one of B, R .and R contain the 6. Compound of the formula group of the formula CO(CH ),,NSO

CN wherein n is an integer from 1 to 6.

2. The compound of claim 1 wherein R is lower al- CH kyl, lower alkylene OH, or lower alkylene 0 Q O'COlower alkyl, R is hydrogen, lower alkyl, 2 lower alkylene OH, lower alkyleneCN, 3

- N-COCH2-N\ lower alkylene 3 O C-CH3 7. Compound of the formula lower alkylene CO lower alkyl or lower alkylene Cl OCO lower alkyl. I

3. The compound of claim 1 wherein B is hydrogen,

chlorine, lower alkyl, lower alkoxy, lower al- 2 kyloylamino or benzoylamino. v

4. Compound of the formula f' 1 i I 8. Compound of the formula cn -cn -cN- C II N CH T C H -0COCH 'N\ l 2 2 CH 1 v V 1 3 v 9. Compound of the formula 5. Compound of the formula v r-- 5 C1 I I. CH- V Y NH-CO-CH NSO CH 

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1 wherein R1 is lower alkyl, lower alkylene -OH, or lower alkylene -O-CO-lower alkyl, R2is hydrogen, lower alkyl, lower alkylene -OH, lower alkylene -CN,
 3. The compound of claim 1 wherein B is hydrogen, chlorine, lower alkyl, lower alkoxy, lower alkyloylamino or benzoylamino.
 4. Compound of the formula
 5. Compound of the formula
 6. Compound of the formula
 7. Compound of the formula
 8. Compound of the formula
 9. Compound of the formula 